CN106824226B - Preparation method and application of carbon-based solid acid - Google Patents
Preparation method and application of carbon-based solid acid Download PDFInfo
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- CN106824226B CN106824226B CN201710026539.8A CN201710026539A CN106824226B CN 106824226 B CN106824226 B CN 106824226B CN 201710026539 A CN201710026539 A CN 201710026539A CN 106824226 B CN106824226 B CN 106824226B
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
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- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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Abstract
The invention belongs to the technical field of biomass catalysis, and particularly relates to a preparation method and application of a carbon-based solid acid, wherein one or more of glucose, fructose, starch and sucrose are used as carbon sources, and a proper amount of liquid acid is added to modify a catalyst to prepare the carbon-based solid acid; the reaction for preparing 5-hydroxymethylfurfural from the prepared carbon-based solid acid by catalyzing carbohydrate has the advantages of mild reaction process, environment-friendly catalyst, simple process, economy, easiness, practicability, provides a new way for industrially preparing the platform compound 5-hydroxymethylfurfural from biomass sugar sources, is favorable for promoting the preparation of petroleum-based chemicals and alternative fuels by using biomass as raw materials, and has strong industrial significance.
Description
Technical Field
The invention belongs to the technical field of biomass catalysis, and particularly relates to a preparation method of carbon-based solid acid catalysis, and a method for preparing 5-Hydroxymethylfurfural (HMF) by selectively converting biomass with a carbon-based solid acid catalyst.
Background
5-hydroxymethylfurfural (abbreviated as HMF) is an important bio-based platform compound, is a key intermediate between biomass chemistry and petroleum-based chemistry, is prepared from biomass serving as a raw material, and is converted into liquid fuel or bulk chemicals, so that the important significance is achieved for relieving increasingly tense fossil resources. The HMF can be converted into 2, 5-dimethylfuran, and the biofuel has better combustion performance and good application prospect. Further oxidizing HMF to obtain 2, 5-diformylfuran and 2, 5-furandicarboxylic acid, wherein the 2, 5-diformylfuran can be used as a pharmaceutical intermediate or a polymer precursor and an antibacterial agent; 2, 5-furandicarboxylic acid can be used as an excellent substitute for terephthalic acid and isophthalic acid as raw materials for producing polyesters (such as PET and PBT); in addition, HMF can be used as a medical intermediate and is widely applied to the cosmetic industry.
HMF as an intermediate has important application prospects in various industries and draws wide attention. Using hexose as a reactant, and carrying out acid catalytic dehydration to obtain HMF; the reactant may be hexose, some oligosaccharide or high polysaccharide, or even raw biomass. The research on the conversion of six-carbon sugar molecules into HMF tends to be mature, and the reaction system and the used catalyst can be classified into homogeneous acid catalysis, ionic liquid catalysis and solid acid catalyst catalysis. Homogeneous acid catalysis, i.e. with some protic acids such as HCl, H3PO4,H2SO4And organic acids such as formic acid, levulinic acid and the like are used as catalysts, a large amount of acid is consumed in the reaction process, a large amount of waste liquid is generated, equipment corrosion and environmental pollution are caused, the catalysts and products are not easy to separate, and a plurality of defects exist in industrial production.
The ionic liquid is a catalytic system which is researched more recently, and the ionic liquid is used as a reaction medium, so that the HMF yield is high. However, since ionic liquids are expensive, post-treatment is difficult, and the toxicity mechanism is not clear, these disadvantages limit the industrial application of ionic liquids.
Compared with liquid acid, the solid acid catalyst has great advantages in product separation, recovery, reutilization and environmental protection. Carbon-based solid acids are receiving more and more attention as a novel solid acid due to higher specific surface area, adjustable pore structure and better chemical stability; in addition, the catalyst material can be obtained by converting cheap and renewable biomass and derivatives thereof, has simple preparation method and low production cost, and has wide application prospect in acid catalytic reactions such as esterification, dehydration, condensation and the like as solid acid.
Disclosure of Invention
The invention aims to overcome the defects of high inorganic acid pollution and high ionic liquid price, provides a preparation method of carbon-based solid acid, and provides a method for preparing 5-Hydroxymethylfurfural (HMF) by catalytically converting a biomass sugar source by using the material. The catalyst is environment-friendly, easy to separate and recycle, can be reused, is simple and easy to operate, and cannot corrode equipment.
According to one aspect of the present invention, there is provided a carbon-based solid acid prepared by the following preparation method:
a) mixing the saccharides with water, putting the mixture into a container, and stirring the mixture for 0.1 to 5 hours at room temperature to ensure that the mixed solid is completely dissolved to form a uniform solution; the amount of water used here is such as to dissolve the saccharides;
b) adding liquid acid into the solution obtained in the step a), and stirring for 0.1-5 h;
c) heat treating the sample obtained in the step b) at 80-200 ℃ for 1-24 h;
d) and C), carrying out heat treatment on the sample prepared in the step C) for 2-24h at the temperature of 200-1100 ℃ in a protective gas atmosphere to obtain the carbon-based solid acid catalyst.
The saccharide in the step a) is one or more of glucose, fructose, sucrose, maltose, lactose, starch or dextrin.
The liquid acid in the step b) is one or more of sulfuric acid, phosphoric acid, hydrochloric acid and nitric acid; the acid is used in a molar ratio of acid to sugar of 0.01-50:1, and the starch or dextrin has a molar weight based on the smallest structural unit C6H10O5Calculating;
wherein the protective gas in the step d) is one of nitrogen, argon and helium.
The carbon-based solid acid catalyst obtained by the invention can be an amorphous carbon-based solid acid or mesoporous carbon solid acid material, or a carbon material in a nano form.
According to another aspect of the invention, the invention provides a method for producing 5-Hydroxymethylfurfural (HMF) from carbon-based solid acid catalyzed biomass:
under the stirring condition in a high-pressure reaction kettle, carbon-based solid acid is used as a catalyst, and biomass is catalyzed in the presence of a solvent to prepare 5-Hydroxymethylfurfural (HMF).
The biomass is one of fructose, glucose, galactose, mannose, sucrose, starch, inulin, corn juice, pretreated cellulose or Jerusalem artichoke juice obtained by squeezing original biomass Jerusalem artichoke tubers.
The solvent is an aqueous system or an anhydrous system, the aqueous system consists of an organic solvent and water, wherein the volume ratio of the aqueous phase to the organic phase is 0.05-20: 1; the organic solvent is methyl isobutyl ketone, n-butanol, 2-butanol, tetrahydrofuran, ethyl acetate, dichloromethane, chloroform, acetone or a mixture in any ratio; the anhydrous system is dimethyl sulfoxide, dimethylformamide, dimethylacetamide, pyrrolidone or a mixture of dimethyl sulfoxide, dimethylformamide, dimethylacetamide and pyrrolidone in any ratio.
The catalytic reaction temperature is 80-300 ℃; the reaction time is 10min-300min, and the stirring speed is 300-1000 rpm.
The weight concentration of the biomass in the reaction system is 0.5-50%; the weight ratio of the biomass to the catalyst is 1-500: 1.
the invention uses sugar and water to form uniform liquid at room temperature, adds liquid acid to stir, and obtains carbon-based solid acid as catalyst after carbonization and high-temperature treatment. The prepared porous carbon material is used for catalyzing carbohydrate to prepare HMF, has the advantages of mild reaction process, environment-friendly catalyst, mild operation condition, simple process and low cost, provides a new way for industrially preparing the platform compound HMF from a biomass sugar source, is beneficial to promoting the preparation of petroleum-based chemicals and alternative fuels by using biomass as a raw material, and has strong industrial significance.
Drawings
Fig. 1 is a TEM image of a phosphorylated carbon solid acid prepared in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention.
The acid used in the invention is a standard acid which is commonly used in a commercial laboratory and is not treated before use.
Example 1
1g of glucose is dissolved in 1mL of deionized water, the solution is stirred for 3h at room temperature, 1.0g of phosphoric acid (85 wt% of commercial phosphoric acid) is added, the stirring is carried out for 2h, then the mixture is dried for 24h at 100 ℃, and the catalyst structure is calcined for 4h at 300 ℃ in a nitrogen atmosphere, and the result is shown in FIG. 1 by using TEM.
Taking 0.2g of the obtained catalyst and 1.2g of fructose, adding 20mL of water and 30mL of sec-butyl alcohol, sealing, reacting at 160 ℃ for 3h, filtering the reaction solution, and detecting by using ion chromatography, wherein the yields of Levulinic Acid (LA) and 5-Hydroxymethylfurfural (HMF) are 6.90% and 89.08% respectively. As can be seen from the experimental results, the phosphorylated carbon-based solid acid has a good effect of catalyzing the conversion of the sugar into the platform compound HMF.
Wherein the LA detection conditions are as follows: mobile phase of 1mM NaOH solution, flow rate of 1.0ml/min, conductivity detector, and chromatographic column of DIONEXIonPac®AS11-HC anion analytical column with detection temperature of 30 deg.CoC, LA retention time is 10 min; the HMF detection conditions are as follows: the mobile phase is 18mM NaOH solution, the flow rate is 1.0ml/min, the pulse amperometric electrochemical detector is a DiONEXCarboPacTMPA1 sugar analysis column, and the detection temperature is 30%oC。
Example 2
Dissolving 1g of fructose in 5mL of deionized water, stirring the solution at room temperature for 3h, adding 1.25g of sulfuric acid, stirring for 2h, drying at 80 ℃ for 24h, and calcining at 300 ℃ for 4h in a nitrogen atmosphere.
Taking 0.2g of the obtained catalyst and 1.2g of fructose, adding 20mL of water and 30mL of sec-butyl alcohol, sealing, reacting at 160 ℃ for 180min, filtering the reaction solution, and detecting by using an ion chromatography, wherein the yields of LA and HMF are respectively 10.27% and 57.20%.
Example 3
Dissolving 1g of glucose in 1mL of deionized water, stirring the solution at room temperature for 3h, adding 0.1g of phosphoric acid, stirring for 2h, drying at 100 ℃ for 12h, and calcining at 300 ℃ for 2h in a nitrogen atmosphere.
Taking 0.2g of the obtained catalyst and 1.2g of glucose, adding 20mL of water and 30mL of sec-butyl alcohol, sealing, reacting at 160 ℃ for 180min, filtering the reaction solution, and detecting by using ion chromatography, wherein the yields of LA and HMF are 5.12% and 54.20% respectively.
Example 4
Dissolving 1g of lactose in 1mL of deionized water, stirring the solution at room temperature for 3h, adding 10g of phosphoric acid, stirring for 2h, drying at 120 ℃ for 6h, and calcining at 800 ℃ for 4h in a nitrogen atmosphere.
Taking 0.2g of the obtained catalyst and 1.2g of glucose, adding 20mL of water and 30mL of sec-butyl alcohol, sealing, reacting at 160 ℃ for 180min, filtering the reaction solution, and detecting by using ion chromatography, wherein the yields of LA and HMF are 5.45% and 75.10% respectively.
Example 5
Dissolving 1g of glucose in 5mL of deionized water, stirring the solution at room temperature for 3h, adding 1.0g of phosphoric acid, stirring for 2h, drying at 200 ℃, and calcining at 200 ℃ for 12h in a nitrogen atmosphere.
Taking 0.02g of the obtained catalyst and 1.2g of glucose, adding 20mL of water and 30mL of sec-butyl alcohol, sealing, reacting at 160 ℃ for 180min, filtering the reaction solution, and detecting by using an ion chromatography, wherein the yields of LA and HMF are 5.25% and 58.27%, respectively.
Example 6
1g of starch sugar is put into 1mL of deionized water, the solution is stirred for 3h at room temperature, 1.0g of phosphoric acid is added, the stirring is carried out for 2h, and then the mixture is dried at 100 ℃ and calcined for 4h in a nitrogen atmosphere at 400 ℃.
Taking 0.2g of the obtained catalyst and 1.2g of glucose, adding 20mL of water and 30mL of sec-butyl alcohol, sealing, reacting at 160 ℃ for 180min, filtering the reaction solution, and detecting by using ion chromatography, wherein the yields of LA and HMF are 6.90% and 58.38% respectively.
Example 7
Dissolving 1g of glucose in 3mL of deionized water, stirring the solution at room temperature for 3h, adding 5.0g of phosphoric acid, stirring for 2h, drying at 80 ℃ for 12h, and calcining at 300 ℃ for 8h in a nitrogen atmosphere.
Taking 0.2g of the catalyst and 0.5g of fructose, adding 10mL of water and 40mL of sec-butyl alcohol, sealing, reacting for 2h at 300 ℃, filtering the reaction solution, and detecting by using ion chromatography, wherein the yields of Levulinic Acid (LA) and 5-Hydroxymethylfurfural (HMF) are respectively 27% and 43%.
Example 8
Dissolving 1g of sucrose in 10mL of deionized water, stirring the solution at room temperature for 1h, adding 10g of phosphoric acid, stirring for 2h, drying at 200 ℃ for 24h, and calcining at 500 ℃ for 8h in a nitrogen atmosphere.
Taking 0.2g of the catalyst and 0.2g of glucose, adding 40mL of water and 10mL of sec-butyl alcohol, sealing, reacting for 3h at 190 ℃, filtering the reaction solution, and detecting by using ion chromatography, wherein the yields of Levulinic Acid (LA) and 5-Hydroxymethylfurfural (HMF) are 35% and 42% respectively.
Example 9
Dissolving 5g of glucose in 20mL of deionized water, stirring the solution at room temperature for 3h, adding 1.0g of phosphoric acid, stirring for 2h, drying at 200 ℃ for 24h, and calcining at 900 ℃ for 2h in a nitrogen atmosphere.
Taking 0.1g of the obtained catalyst and 1.2g of inulin, adding 20mL of water and 30mL of sec-butyl alcohol, sealing, reacting at 120 ℃ for 3h, filtering the reaction solution, and detecting by ion chromatography, wherein the yields of Levulinic Acid (LA) and 5-Hydroxymethylfurfural (HMF) are respectively 20% and 63%.
Example 10
Slowly dissolving 5g of glucose in 1mL of deionized water, stirring the solution at room temperature for 3h, adding 1.0g of nitric acid, stirring for 2h, drying at 80 ℃ for 24h, and calcining at 300 ℃ for 24h in a nitrogen atmosphere.
Taking 0.5g of the obtained catalyst and 1.2g of sucrose, adding 50ml of dimethylformamide, sealing, reacting at 80 ℃ for 3h, filtering the reaction solution, and detecting by using ion chromatography, wherein the yields of Levulinic Acid (LA) and 5-Hydroxymethylfurfural (HMF) are respectively 2% and 45%.
Example 11
Dissolving 1g of fructose in 1mL of deionized water, stirring the solution at room temperature for 3h, adding 1.0g of hydrochloric acid, stirring for 2h, drying at 100 ℃ for 24h, and calcining at 200 ℃ for 4h in a nitrogen atmosphere.
Taking 0.002g of the obtained catalyst and 1.0g of fructose, adding 20mL of water and 30mL of sec-butyl alcohol, sealing, reacting for 3h at 160 ℃, filtering the reaction solution, and detecting by using ion chromatography, wherein the yields of Levulinic Acid (LA) and 5-Hydroxymethylfurfural (HMF) are respectively 5% and 38%.
Example 12
Dissolving 1g of glucose in 1mL of deionized water, stirring the solution at room temperature for 3h, adding 1.0g of phosphoric acid, stirring for 2h, drying at 100 ℃ for 24h, and calcining at 300 ℃ for 4h in a nitrogen atmosphere.
Taking 0.5g of the obtained catalyst and 0.5g of fructose, adding 50ml of dimethyl sulfoxide, sealing, reacting at 80 ℃ for 3 hours, filtering the reaction solution, and detecting by using ion chromatography, wherein the yields of Levulinic Acid (LA) and 5-Hydroxymethylfurfural (HMF) are respectively 7% and 55%.
Example 13
Dissolving 3g of fructose in 1mL of deionized water, stirring the solution at room temperature for 3h, adding 3g of sulfuric acid, stirring for 2h, drying at 100 ℃ for 24h, and calcining at 1100 ℃ for 4h in a nitrogen atmosphere.
Taking 0.1g of the obtained catalyst and 1.2g of fructose, adding 50ml of dimethylformamide, sealing, reacting at 80 ℃ for 3 hours, filtering the reaction solution, and detecting by using ion chromatography, wherein the yields of Levulinic Acid (LA) and 5-Hydroxymethylfurfural (HMF) are respectively 3% and 69%.
The porous carbon solid acid material prepared by the invention has good catalytic effect on the conversion of the biomass sugar into the bio-based platform compound 5-hydroxymethylfurfural. Compared with other solid acid catalysts, the catalyst precursor is a renewable carbon source, the source is wide, the cost is low, the catalyst is easy to obtain, and the preparation method of the catalyst is simple and has good industrial application prospect.
Although the embodiments of the present invention have been described in detail, it should be understood that various changes, substitutions, and alterations can be made hereto without departing from the spirit and scope of the invention.
Claims (6)
1. A preparation method of carbon-based solid acid comprises the following steps:
a) mixing sugar and water, placing in a container, stirring at room temperature for 0.1-5h to completely dissolve sugar to form a uniform solution;
b) adding liquid acid into the solution obtained in the step a), and continuously stirring for 0.1-5 h;
c) carrying out heat treatment on the sample obtained in the step b) at the temperature of 80-200 ℃ for 1-24 h;
d) carrying out heat treatment on the sample prepared in the step c) for 2-24h at the temperature of 200-1100 ℃ in a protective gas atmosphere to obtain carbon-based solid acid; the carbon-based solid acid is amorphous carbon-based solid acid or mesoporous carbon solid acid or carbon solid acid in a nano form;
the liquid acid in the step b) is one or more of sulfuric acid, phosphoric acid, hydrochloric acid and nitric acid.
2. Use of a carbon-based solid acid prepared by the method of claim 1, wherein: under the stirring condition in a high-pressure reaction kettle, carbon-based solid acid is used as a catalyst, and biomass is catalyzed in the presence of a solvent to prepare 5-hydroxymethylfurfural.
3. Use according to claim 2, characterized in that: the biomass is one of fructose, glucose, galactose, mannose, sucrose, starch, inulin, corn juice, pretreated cellulose and Jerusalem artichoke juice obtained by juicing original biomass Jerusalem artichoke tubers.
4. Use according to claim 3, characterized in that: the solvent is an aqueous system or an anhydrous system, the aqueous system consists of an organic solvent and water, wherein the volume ratio of the aqueous phase to the organic phase is 0.05-20: 1; the organic solvent is any one or more of methyl isobutyl ketone, n-butanol, 2-butanol, tetrahydrofuran, ethyl acetate, dichloromethane, chloroform and acetone; the anhydrous system is any one or more of dimethyl sulfoxide, dimethylformamide, dimethylacetamide and pyrrolidone.
5. Use according to claim 3, characterized in that: the reaction temperature is 80-300 ℃, the reaction time is 10-300 min, and the stirring speed is 300-1000 rpm.
6. Use according to claim 3, characterized in that: the weight concentration of the biomass in the reaction system is 0.5-50%; the weight ratio of the biomass to the catalyst is 1-500: 1.
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CN108940313B (en) * | 2018-07-17 | 2020-08-25 | 中国科学技术大学 | Biomass carbon-based solid acid catalyst and preparation method and application thereof |
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